Secondary xenoxy-alkyl-amines



Patented Au 19, 194i 2,252,828 SECONDARY xENoxY-ALKrL-AMmEs STATES PATENT ounce Francis N. Alquist and Harold R. Slagh, Midland,

Micln, assignors to The Dow Chemical Qompany, Midland, Mich a corporation oi. Michi- No Drawing, Application April 19, 1939,

Serial No, 268,824

9 Claims. (01. also-e71) This. invention concerns certain secondary amines having the ionnula wherein R represents a xenyl radical, R. represents a lower alkylene group, and R" represents an oxygen-containing radical such as hydroxy:

aryl, hydroxy-alkyl, alkoxy-aryl, alkoxy-alkyl, aryloxy-aryl, aryloxy-alkyl, and furfuryl radicals and wherein all substituted aryl groups, as desigand the hydrochlorides thereof.

Our new secondary amines can be prepared by pounds, readily separable from such solvent suspension by filtration.

If desired, the condensation may be carried out in the presence of an inert organic solvent such as xylene, toluenejand the like. Also, a small amount of copper or potassium iodide cataa lyst may be included in the reaction mixture to nated by R", are membersof the benzene series,

heating a mixture of a xenoxy-alkyl halide and a suitable primary amine to reaction temperature and thereafter separating out. the desired secondary amine compound. We generally employ an appreciable excess of the primary amine in order that the major product of reaction can be the secondary amine compound. The reaction is carriedout in the liquid phase under atmospheric pressure or.. in a high pressure reaction und'er .autogenous pressure, stirring being maintained throughout-the process until the 'condensation'is complete. The preferred temperature is dependout upon the. particular reactants employed and is usually between about 125 C. and the decomposition temperature of the reaction mixture, al-

though somewhat lower temperatures will somee times accomplish the condensation. v On completion of the heating step, the-reaction mixture may be washedgwith, aqueous alkali or otherwise neutralizedto liberate the free amine compound.

While the crude product so ;-obtai ned has been found of value as an. acid inhibitor, such mixture may be fractionally distilled under reduced pres-' sure to obtain the desired secondaryamines in desired form. These'compounds are for the most part high-boiling oils diflicultly soluble in water, somewhat soluble in most organic solvents and having a; characteristic amine odor. The resinous tars obtained as distillation residues following the recovery of the secondary amines consist of a mixture of tertiary amine products which decompo'se upon attempted distillation;

The hydrochlorides olthe secondary amine compounds obtained 'as described above may be readily preparedby dissolving secondary amine in a suitable organic solvent, e. .g. benzene, pe-

troleum ether, and the like, and thereafter bubbling dry hydrogen chloride through the solution to precipitate the desired amine salts. These hydrochlorides are generally solid, crystalline comaccelerate the speed of reaction, although this is 'not required. Similarly, inorganic alkalies,

The xenoxy-alkyl halides employed'as reactants in the preparation of our new secondary amines and their hydrohalides may be prepared by the reaction of an alkylene dihalide with an alkali metal xenolate, e. g. sodium-orthophenylphenolate.

The .xenoxy-alkyl halides are all high-boiling compounds and vary in characteristic from viscous oils to high-melting solids.

The following examplesdescribe in detail several adaptations of our invention, but are not to be construed as limiting the same:

Emample 1 116 grams (0.5 mol) of beta-2 xenoxy-ethyl chloride and 120 grams (1.1 mol) of .Z-aminophenol were dissolved in milliliters of'xylene' and the solution refluxed at 1469-157 C. for 310. hours. 220 grams of alil per cent aqueous sodium hydroxide solution was then shaken with the reacted mixture and the xylene layer separated. Upon distillation of the xylene solution, there was obtained 71 grams of beta-Z-xenoxyethyl) (Z-hydroxy-phenyl) 'amine as a thick, straw-colored sirup boiling between 210 and 224- C. at 0.2 inch pressure This compound is soluble in alcohol and benzene and has the formula IIL.

Erample 2 116 grams (0.5 mol) of beta-2-xenoxy ethyl This compound is a straw-colored oil boiling at 220 to 227 C. at 0.1 inch pressure and tending to crystallize out upon long standing.

A portion of this product was dissolved in benzene and reacted with an excess of dry hydrogen chloride, whereby a white, crystalline precipitate was formed. This product was filtered out of the benzene medium and washed with petroleum droxy-ethyl) amine hydrochloride as a white, crystalline product melting at 149.5 C.

In a similar manner, other xenoxy-alkyl halides, such as the bromides and iodides, may be reacted with primary amines to form secondary amine compounds falling within the scope of this invention. Representative of the xenoxy-alkyl halides which may be so reacted are beta-3- xenoxy-ethyl chloride boiling at 179 to 181C. at 5 millimeters pressure; beta-.2-xenoxy-norma1- propyl chloride having a specific gravity of 1.141

. at 20/4 C. and boiling at 147 to 149 C. at 3- millimeters pressure; beta-Z-xenoxy-ethyl bromide, a white, crystalline solid melting at 166.5 C.

ether to obtain (beta-2-xenoxy-ethyD-(beta-hy solution of (beta-Z-xenoxy-ethyl) (Z-hydtoxyphenyl) amine in 6 per cent hydrochloric acid was prepared. Weighed iron strips of 6.75 square inches surface area were suspended in this solution and also in a control solution of 6 per cent hydrochloric acid to determine the inhibiting ei-.

fect of the amine. After 16 hours at room temperature, the test specimens suspended in the control solution were found to have lost an average of 6.66 grams in weight, respectively. Similar test specimens suspended in the hydrochloric acid-amine solution showed an average weight loss of 0.86 gram after 16hours. The presence of the aminefraction in the aqueous acid solu-- tion resulted, therefore, in a reduction in excess of 87 per cent of the total weight lost by corrosion. In a similar test, a 1 per cent mixture of (beta-2-xenoxy-ethyl)(beta-hydroxy-ethyl) amine and hydrochloric acid gave a comparable reduction in the amount of iron dissolved by the treating acid.

The present application is a continuation-inpart of our co-pending application Serial No. 221,605, filed July 27, 1938.

We claim:

1. A compound selected from the group consisting of (1) secondary amines having the and boiling at 170 to 175 C. at 5 millimeters pressure; beta-4-xenoxy-ethyl chloride, a crystalline compound melting at 130C. and boiling at l6-3 to 165 C. at 8 millimeters pressure; (betam'ethyl) (gamma-Z-xenoxy) -n-propyl chloride, an oil boiling at 170 to173 C. at 5 millimeters pressure; 'beta-2-(5-chloro-xenoxy)-ethy1 chloride, a

viscous oil boiling at 149150 C. at 3 millimeters pressure; 1 beta-2- (5-isopropyl-xenoxy) -e t h y l chloride, an oil boiling at 150 to 153 C, at 2 millimeters pressure, and having aspeciflc gravity-of 1.093 at -20 0.; etc. Qther similar compounds which maybe employed are omega-2- xenoxy-n-amyl chloride, gamma-2-bromo-xen oxy-propyl bromide, beta-2- (S-te rtiary-butylxenoxy) -ethyl ride, and the like. Among other oxygen-contain ing amines which may be reacted'with such xenoxy-alkyl halides are: furfuryl amine, 2-cyclohexyl-4-amino-phenol; 4-methyl-2-amino phenol, 3amino-phenol, 2-hydroxypropyl amine, 4-hydroxy-butyl amine, ethoxy-ethyl amine, propoxy-propyl amine,'butoxy-ethyl amine, phenoxy chloride, beta-zj-xenoxy-ethyl iodide, beta-4-(2,6-dimethy1-xenoxy) -ethyl chic-- formula H R o R'-1 I-,R" wherein R. represents a xenyl radical, R represents a lower alkylene group, and R" represents an oxygen containing organic residue selected from the group consisting of hydroxy- -aryl, hydroxy-alkyl, alkoxy-aryl, alkoxy-alkyl, aryloxyaryl, aryloxy-alkyl, and furfuryl, radicals and wherein all substituted aryl groups, as designated by R", are members of the benzene series, and (2) the hydrochlorides thereof.

2. A secondary amine having the formula H I RORI!I'-R" wherein R represents a xenyl radical, R represents a lower alkylene group, and R. represents an oxygen-containing organic residue selected from the group consisting of hydroxy-aryl, hydroxy-alkyl, alkoxy-aryl, alkoxy-alkyl, aryloxyaryl, aryloxy-alkyl, and furiuryl radicals and whereinall substituted aryl groups, as designated by R", are members of the benzene series.

3. An amine hydrochloride having the formula aryl, aryloxy-alkyl, and furfuryl radicals and,

' wherein all substituted aryl groups, as designated by R", are members of the benzene series.

4. A secondary amine having the formula R0-RN-R" wherein R represents a xenyl, radical, R represents a lower alkylene group, and R" represents a hydroxy-aryl radical of the benzene series. 5. A secondary amine having the formula wherein R represents a xenyl radical, R represents a lower alkylene group, and R" represents a h'ydroxy-alkyl radical.

6. A secondary amine having the formula H 'R0-C:Hal q'-R" wherein R represents a xenyl radical, and R" represents an oxygen-containing organic residue selected from the group consisting of hydroxyaryl, hydroxy-alkyl, alkoxy-aryl, alkoxy-alkyl,

aryloxy-aryl, aryloigv-alkyl, and furfuryl radicals and wherein all substituted aryl groups, as designated by R",- are members of the benzene series.

7. A secondary amine having the formula 

